Process for preventing, reducing and removing hard-water scale employing methylol pheol derivatives



United States Patent PROCESS FOR PREVENTING, REDUQING AND REMOVING HARD-WATER SALE EMPLOYING METHYLOL PHENOL DERIVATIVES Melvin De Groote, St. Louis, and Ewan-ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, a corporation of Delaware No Drawing. Original application May 12, 1960, Ser. No. 28,514. Divided and this application Apr. 11, 1961, Ser. No. 102,093

17 Claims. (Cl. 252-180) This application is a division of our copending application Serial No. 28,514, filed May 12, 1960, which latter application is a continuation-in-part of our copending application Serial No. 730,510, filed April 24, 1958, now abandoned. See also our copending application Serial No. 799,488, filed March 16, 1959, now abandoned, which is a division of Serial No. 730,510. This invention relates to a process for preventing, reducing and removing the deposition of hard-water scale employing 1) oxyalkylated, (2) acylated, (3) oxyalkylated then acylated, (4) acylated then oxyalkylated, and (5) acylated, then oxyalkylated and then acylated, monomeric polyamino methyl phenols. These substituted phenols are produced by a process which is characterized by reacting a preformed methylol phenol (i.e. formed prior to the addition of the polyamine) with at least one mole of a secandary polyamine per equivalent of methylol group on the phenol, in the absence of an extraneous catalyst (in the case of an aqueous reaction mixture, the pH of the reaction mixture being determined solely by the methylol phenol and the secondary polyamine), until about one mole of water per equivalent of methylol group is removed; and then reacting this product with (1) an oxyalkylating agent, (2) an acylating agent, (3) an oxyalkylating agent then an acylating agent, (4) an acylating agent then an oxyalkylating agent or (5) an acylating agent then an oxyalkylating agent and then an acylating agent.

The reasons for the unexpected monomeric form and properties of the polyaminomethyl phenol are not understood. However, we have discovered that when 1) a preformed methylolphenol (i.e. formed prior to the addition of the polyamine) employed as a starting material is reacted with (2) a polyamine which contains at least one secondary amino group (3) in amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol, (4) in the absence of an extraneous catalyst, until (5) about one mole of water per equivalent of methylol group is removed, then a monomeric polyaminomethyl phenol is produced which is capable of being oxyalkylated, acylated, oxyalkylated then acylated, or acylated than oxyalkylated, or acylated, then oxyalkylated and then acylated to provide the superior products employed in the process of this invention. All of the above five conditions are critical for the production of these monomeric polyaminomethyl phenols.

In contrast, if the methylol phenol is not preformed but is formed in the presence of the polyamine, or the preformed methylol phenol is condensed with the polyamine in the presence of an extraneous catalyst, either acidic or basic, for example, basic or alkaline materials such as NaOH, Ca(Ol-l) Na CO sodium methylate,

3,148,150 Patented Sept. 8, 1964 etc., a polymeric product is formed. Thus, if an alkali metal-phenate is employed in place of the free phenol, or even if a lesser quantity of alkali metal is present than is required to form the phenate, a polymeric product is formed. Where a polyamine containing only primary amino groups and no secondary amino groups is reacted with a methylol phenol, a polymeric product is also produced. Similarly, where less than one mole of secondary amine is reacted per equivalent of methylol group, a polymeric product is also formed.

In general, the monomeric polyarninomethyl phenols are prepared by condensing the methylol phenol with the secondary amine as disclosed above, said condensation being conducted at a temperature sufiiciently high to eliminate water but below the pyrolytic point of the reactants and product, for example, at to 200 C., but preferably at to C. During the course of the condensation water can be removed by any suitable means, for example, by use of an azeotroping agent, reduced pressure, combinations thereof etc. Measuring the water given off during the reaction is a convenient method of judging completion of the reaction.

The classes of methylol phenols employed in the condensation are as follows:

M 0n0phenols.A phenol containing 1,2 or 3 methylol groups in the ortho or para position (i.e. the 2,4,6 positions), the remaining positions on the ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, and alkoxy, etc., groups, and having but one nuclear linked hydroxyl group.

Diphen0Is.Gne type is a diphenol containing two hydroxybenzene radicals directly joined together through the ortho or para (i.e. 2,4, or 6) position with a bond joining the carbon of one ring with the carbon of the other ring, each hydroxybenzene radical containing 1 to 2 methylol groups in the 2,4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyamine-rnethylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.

A second type is a diphenol containing two hydroxybenzene radicals joined together through the ortho or para (i.e. 2,4, or 6 position) with a bridge joining the carbon of one ring to a carbon of the other ring, said bridge being, for example, alkylene, alkylidene, oxygen, carbonyl, sulfur, sulfoxide and sulfone etc., each hydroxybenzene radical containing 1 to 2 methylol groups in the 2,4, or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyaminomethylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.

The secondary polyamines employed in producing the condensate are illustrated by the following general formula:

where at least one of the Rs contains an amino group and the Rs contain alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl radicals, and the corresponding radicals containing heterocyclic radicals, hydroxy radicals, etc. The Rs may also be joined together to form heterocyclic polyamines. The preferred classes of polyamines are the alkylene polyarnines, the hydroxylated alkylene polyamines, branched polyamines containing at least three primary amino groups, and polyamines containing cyclic amidine groups. The only limitation is that there shall be present in the polyamine at least one secondary amino group which is not bonded directly to a negative radical which reduces the basicity of the amine, such as a phenyl group.

An unusual feature of the products employed in the process of the present invention is the discovery that methylol phenols react more readily under the herein specified conditions with secondary amino groups than with primary amino groups. Thus, where both primary and secondary amino groups are present in the same molecule, reaction occurs more readily with the secondary amino group. However, where the polyarnino contains only primary amino groups, the product formed under reaction conditions as mentioned above is an insoluble resin. In contrast, where the same number of primary amino groups are present on the amine in addition to at least one secondary amino group, reaction occurs predominantly With the secondary amino group to form non-resinous derivatives. Thus, where trimethylol phenol is reacted with ethylene diamine, an insoluble resinous composition is produced. However, where diethylene triamine, a compound having just as many primary amino groups as ethylene diamine, is reacted, according to this invention a non-resinous product is unexpectedly formed.

The term monomeric as employed in the specification and claims refers to a polyaminomethylphenol containing within the molecular unit one aromatic unit corresponding to the aromatic unit derived from the starting methylol phenol and one polyamine unit for each methylol group originally in the phenol. This is in contrast to a polymeric or resinous polyaminomethyl phenol containing within the molecular unit more than one aromatic unit and/ or more than one polyamino unit for each methylol group.

The monomeric products produced by the condensation of the methylol phenol and the secondary amine may be illustrated by the following idealized formula:

where A is the aromatic unit corresponding to that of the methylol reactant, and the remainder of the molecule is the polyaminomethyl radical, one for each of the original methylol groups.

This condensation reaction may be followed by oxyalkylation in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide, glycide, methylglycide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions or propylene oxide and ethylene oxide, or smaller proportions thereof in relation to the methylol phenol-amine condensation product. Thus, the molar ratio of alkylene oxide to amine condensate can range Within wide limits, for example, from a 1:1 mole ratio to a ratio of 1000:1, or higher, but preferably 1 to 200. By proper control, desired hydrophilic or hydrophobic properties are imparted to the composition. As is well known, oxyalkylation reactions are conducted under a wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc. For instance oxyalkylation reactions can be carried out at temperatures of from 200 C., and pressures of from 10 to 200 p.s.i., and times of from 15 min. to several days. Preferably oxyalkylation reactions are carried out at 80 to C. and 10 to 30 psi. For conditions of oxyalkylation reactions see US. Patent 2,792,369 and other patents mentioned therein.

As in the amine condensation, acylation is conducted at a temperature sufiiciently high to eliminate Water and below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from to 280 C., but preferably at 140 to 200 C. In acylating, one should control the reaction so that the phenolic hydroxyls are not acylated. Because acyl halides and anhydrides are capable of reacting with phenolic hydroxyls, this type of acylation should be avoided. It should be realized that either oxyalkylation or acylation can be employed alone or each alternately, either one preceding the other. In addition, the amine condensate can be acylated, then oxyalkylated and then reacylated. The amount of acylation agent reacted will depend on reactive groups or the compounds and properties desired in the final product, for example, the molar ratios of acylation agent to amine condensate can range from 1 to 15, or higher, but preferably 1 to 4.

Where the above amine condensates are treated with alkylene oxides, the product formed will depend on many factors, for example, whether the amine employed is hydroxylated, etc. Where the amines employed are non-hydroxylated, the amine condensate is at least susceptible to oxyalkylation through the phenolic hydroxyl radical. Although the polyarnine is non-hydroxylated, it may have one or more primary or secondary amino groups which may be oxyalkylated, for example, in the case of tetraethylene pentamine. Such groups may or may not be susceptible to oxyalkylation for reasons which are obscure. Where the non-hydroxylated amine contains a plurality of secondary amino groups, wherein one or more is susceptible to oxyalkylation, or primary amino groups, oxyalkylation may occur in those positions. Thus, in the case of the non-hydroxylated polyamines oxyalkylation may take place not only at the phenolic hydroxyl group but also at one or more of the available amino groups. Where the amine condensate is hydroxyalkylated, this latter group furnishes an additional position of oxyalkylation susceptibility.

The product formed in acylation will vary with the particular polyaminomethyl phenol employed. It may be an ester or an amide depending on the available reactive groups. If, however, after forming the amide at a temperature between 140-250 C., but usually not above 200 C., one heats such products at a higher range, approximately 250-280" C., or higher, possibly up to 300 C. for a suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of Water for each mole of carboxylic acid employed, the first mole of water being evolved during amidification. The product formed in such cases is believed to contain a cyclic amidine ring such as an imidazoline or a tetrahydropyrimidine ring.

Ordinarily the methods employed for the production of amino imidazolines result in the formation of substan tial amounts of other products such as amido imidazolines. However, certain procedures are well known by which the yield of amino imidazolines is comparatively high as, for example, by the use of a polyarnino in which one of the terminal hydrogen atoms has been replaced by a low molal alkyl group or an hydroxyalkyl group, and by the use of salts in which the polyamine has been converted into a rnonosalt such as combination with hydrochloric acid or paratoluene sulfonic acid. Other procedures involve reaction with a hydroxyalkyl ethylene diamine and further treatment of such imidazoline having a hydroxyalkyl substituent with two or more moles of ethylene imine. Other well known procedures may be employed to give comparatively high yields.

Other very useful derivatives comprise acid salts and quaternary salts, derived therefrom. Since the compositions contain basic nitrogen groups, they are capable of reacting with inorganic acids, for example hydrohalogens (HCl, HBr, HI), sulfuric acid, phosphoric acid, etc., aliphatic acids (acetic, propionic, glycolic, diglycolic, etc.), aromatic acids (benzoic, salicylic, phthalic, etc.), and organic compounds capable of forming salts, for example, those having the general formula RX wherein R is an organic group, such as an alkyl group (e.g. methyl, ethyl, propyl, butyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, oleyl, octadecyl etc.) cycloalkyl (e.g. cyclopentyl, cyclohexyl, etc.), aralkyl (e.g. benzyl,

etc.), and the like, and X is a radical capable of forming a salt such as those derived from acids (e.g. halide, sulfate, phosphate, sulfonate, etc., radicals). The preparation of these salts and quaternary compounds is Well known to the chemical art. For example, they may be prepared 'by adding suit-able acids (for example, any of those mentioned herein as acylating agents) to solutions of the basic composition or by heating such compounds as alkyl halides with these compositions. 'Diacid and quaternary salts can also be formed by reacting alkylene dihalides, polyacids, etc. The number of moles of acid and quaternary compounds that may react with the composition of this invention will, of course, depend on the number of basic nitrogen groups in the molecule. These salts may be represented by the general formula N+ X1 wherein N comprises the part of the compound containing the nitrogen group which has been rendered positively charged by the H or R of the alkylating compound and X represents the anion derived from the alkylating compound.

THE METHYLOL PHENOL As previously stated, the methylol phenols include monophenols and diphenols. The methylol groups on the phenol are either in one or two ortho positions or in 40 the para position of the phenolic rings. The remaining phenolic ring positions are either unsubstituted or substituted with groups not interfering with the amine methylol condensation. Thus, the monophenols have 1, 2 or 3 methylol groups and the diphenols contain 1, 2, 3 or 4 methylol groups.

The following is the monophenol most advantageously employed:

HOOH CHQOH I CHzOH This compound, 2,4,6 trimethylol phenol (TMP) is available commercially in 70% aqueous solutions. The designation TMP is sometimes used to designate trimethylol propane. Apparently no confusion is involved, in light of the obvious difierences.

A second monophenol which can be advantageously employed is:

where R is an aliphatic saturated or unsaturated hydrocarbon having, for example, 1-30 carbon atoms, for eX- ample, methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl,

6 amyl, tort-amyl, hexyl, tert-hexyl, octyl, nonyl, decyl, dodecyl, octo-decyl, etc., the corresponding unsaturated groups, etc. I

The third monophenol advantageously employed is:

HOCHz OHQOH lHg O H where R comprises an aliphatic saturated or unsaturated hydrocarbon as stated above in the second monophenol, for example, that derived from cardanol or hydrocardanol.

The following are diphenol species advantageously employed:

One species is ornoH on a no. i -OH I R ornon omen where R is hydrogen or a lower alkyl, preferably methyl.

A second species is where R has the same meaning as that of the second species of the monophenols and R is hydrogen or a lower alkyl, preferably methyl.

We can employ a wide variety of methylol phenols in the reaction, and the reaction appears to be generally applicable to the classes of phenols heretofore specified. Examples of suitable methylol phenols include:

Monophenols:

Z-methylol phenol Diphenols:

(EH20 H (EH: 0 H C -C CHrOH CHzOH CH2OH CH2OH CH3 CH:

CHzOH CH2OH CH OH CH3 CH3 0112011 JHZOH CHzOH HOCH CH2 CH2OH CHZOH CHZOH OH DE E om-omU-cmon l 12 Cn zs OH OH $53 HO CH 'C- CHZOH he.

OH2OH CHzOH OH OH G3 l HO-CH2 (|J CH2OH CH 1 CH3 CH3 OHzOH CHzOH l I a I CH3 CHzOH CHzOH $H2OH CHrOH /H2011 CHzOH CHBOH CHZOH ii HzOH CHZOH OH OH I I no orrQ-mO-cmon CmHzs 2E25 CHZOH CHzOH ii CHzOH CHzOH OHzOH OHzOH onion CHzOH C IH2OH CHzOH Examples of additional methylol phenols which can be employed to give the useful products of this invention are described in The Chemistry of Phenolic Resins, by Robert W. Martin, Tables V and VI, pp. 32-39 (Wiley,- 1956).

THE POLYAMINE As noted previously, the general formula for the polyamine is R HN This indicates that a wide variety of reactive secondary polyamines can be employed, including aliphatic p0lyamines, cycloaliphatic polyamines, aromatic polyamines (provided the aromatic poly-amine has at least one secondary amine which has no negative group, such as a phenyl group directly bonded thereto) heterocyclic polyarnines and polyamines containing mixtures of the above groups. Thus, the term polyamine includes compounds having one amino group on one kind of radical, for example, an aliphatic radical, and another amino group on the heterocyclic radical as in the case of the following formula:

provided, of course, the polyamine has at least one secondary amino group capable of condensing with the methylol group. It also includes compounds which are totally heterocyclic, having a similarly reactive secondary amino group. It also includes polyamines having other elements besides carbon, hydrogen and nitrogen, for example, those also containing oxygen, sulfur, etc. As prepreviously stated, the preferred embodiments of the pressent invention are the alkylene polyamines, the hydroxylated alkylene polyamines and the amino cyclic amidines.

Polyamines are available commercially and can be prepared by Well-known methods. It is Well known that olefin dichlorides, particularly those containing from 2 to 10 carbon atoms, can be reacted with ammonia or amines to give alkylene polyamines. If, instead of using ethylene dichloride, the corresponding propylene, butylene, amylene or higher molecular weight dichlorides are used, one then obtains the comparable homologues. One can also use alpha-omega dialkyl ethers such as CICH OCH CI; CICH CH OCH CH CL and the like. Such polyamines can be alkylated in the manner commonly employed for alkylating monoamines. Such alkylation results in products which are symmetrically or nonsymmetn'cally alkylated. The symmetrically alkylated polyarnines are most readily obtainable. For instance, alkylated products can be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, amyl chloride, cetyl chloride, and the like and a polyamine having one or more primary amino groups. Such reactions result in the formation of hydrochloric acid, and hence the resultant product is an amine hydrochloride. The conventional method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group, but as a matter of fact, the radical introduced can be characterized by a carbon atom chain interrupted at least once by an oxygen atom. In other Words, alkylation is accomplished by compounds which are essentially alkyoxyalkyl chlorides, as, for example, the following:

The reaction involving the alkylene dichlorides is not limited to ammonia, but also involves amines, such as ethylamine, propylamine, butylarnine, octylamine, decylamine, cetylamine, dodecylamine, etc. Cycloaliphatic and aromatic amines are also reactive. Similarly, the reaction also involves the comparable secondary amines, in which various alkyl radicals previously mentioned appear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octylarnine, etc. Furthermore, compounds derived by reactions involving al kylene dichlorides and a mixture of ammonia and amines, or a mixture of two different amines are useful. However, one need not employ a polyamine having an alkyl radical. For instance, any suitable polyalkylene polyamine, such as an ethylene polyamine, a propylene polyamine, etc., treated with ethylene oxide or similar oxyalkylating agent are useful. Furthermore, various hydroxylated amines, such as monoethanolamine, monopropanolamine, and the like, are also treated with a suitable alkylene dichloride, such as ethylene dichloride, propylene dichloride, etc.

As to the introduction of a hydroxylated group, one can use any one of a number of well-known procedures such as alkylation, involving a chlorhydrin, such as ethylene chlorhydrin, glycerol chlorhydrin, or the like. Such reactions are entirely comparable to the alkylation reaction involving alkyl chlorides previously described. Other reactions involve the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide or the like. Glycide is advantageously employed. The type of reaction just referred to is well known and results in the introduction of a hydroxylated or polyhydroxylated radical in an amino hydrogen position. It is also possible to introduce a hydroxylated oxyhydrocarbon atom; for instance, instead of using the chlorhydrin corresponding to ethylene glycol, one employs the chlorhydrin corresponding to diethylene glycol. Similarly, instead of using the chlorhydiin corresponding to glycerol, one employs the chlorhydrin corresponding to diglycerol.

From the above description it can be seen that many of the above polyamines can be characterized by the genwhere the Rs, which are the same or different, comprise hydrogen, alkyl, cycloalkyl, aryl, alkyloxyalkyl, hydroxylated alkyl, hydroxylated alkyloxyalkyl, etc., radicals, x is zero or a Whole number of at least one, for example 1 to 10, but preferably 1 to 3, provided the polyamine contains at least one secondary amino group, and n is a whole number, 2 or greater, for example 2-10, but preferably 2-5. Of course, it should be realized that the amino or hydroxyl group may be modified by acylation to form amides, esters or mixtures thereof, prior to the methylol-amino condensation provided at least one active secondary amine group remains on the molecule. Any of the suitable acylating agents herein described may be employed in this acylation. Prior acylation of the amine can advantageously be used instead of acylation subsequent to amine condensation.

A particularly useful class of polyamines is a class of branched polyamines. These branched polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene itlas ps g NH z A N s Y wherein R is an alkylene group such as ethylene, propylene, butylene and other homologues (both straight chained and branched), etc., but preferably ethylene; and x, y and z are integers, x being for example, from 4 to 24 or more but preferably 6 to 18, y being for example 1 to 6 or more but preferably 1 to 3, and z being for example O6 but preferably 0-1. The x and y units may be sequential, alternative, orderly or randomly distributed.

The preferred class of branched polyamines includes those of the formula where n is an integer, for example l-2O or more but preferably 1-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched.

The particularly preferred branched polyamines are presented by the following formula:

The radicals in the brackets may be joined in a headto-head or a head-to-tail fashion. Compounds described by this formula wherein n=13 are manufactured and sold by Dow Chemical Company as Polyamines N-400, N-800, N-1200, etc. Polyarnine N-400 has the above formula wherein n=1 and was the branched polyamine employed in all of the specific examples.

The branched polyamines can be prepared by a wide variety of methods. One method comprises the reaction of ethanolamine and ammonia under pressure over a fixed bed of a metal hydrogenation catalyst. By controlling the conditions of this reaction one can obtain various amounts of piperazine and polyamines as Well as the branched chain polyalkylene polyamine. This process is described in Australian Patent No. 42,189 and in the East German Patent 14,480 (March 17, 1958) reported in Chem. Abstracts, August 10, 1958, 14129.

The branched polyamines can also be prepared by the following reactions:

The above polyamines modified with higher molecular weight aliphatic groups, for example, those having from Variations on the above procedure can produce other branched polyamines.

The branched nature of the polyamine imparts unusual properties to the polyamine and its derivatives. Cyclic aliphatic polyamines having at least one secondary amino group such as piperazine, etc., can also be employed.

It should be understood that diamines containing a secondary amino group may be employed. Thus, where x in the linear polyalkylene amine is equal to zero, at least one of the Rs would have to be hydrogen, for example, a compound of the following formula:

Suitable polyamines also include polyamines wherein the alkylene group or groups are interrupted by an oxygen radical, for example,

or mixtures of these groups and alkylene groups, for example,

R R R R X R where R, n and x has the meaning previously stated for the linear polyamine.

For convenience the aliphatic polyamines have been classified as nonhydroxylated and hydroxylated alkylene polyamino amines. The following are representative members of the nonhydroxylated series:

Diethylene triamine, Dipropylene triamine, Dibutylene triamine, etc. Triethylene tetramine, Tripropylene tetramine, Tributylene tetramine, etc., Tetraethylene pentamine, Tetrapropylene pentamine, Tetrabutylene pentamine, etc., Mixtures of the above,

Mixed ethylene, propylene, and/or butylene, etc., polyamines and other members of the series.

830 or more carbon atoms, a typical example of which is Where R is alkyl and Z is an alkylene group containing phenyl groups on some of the alkylene radicals since the phenyl group is not attached directly to the secondary amino group.

In addition, the alkylene group substituted with a hydroxy group is reactive.

Polyamines containing aromatic groups in the main part of the chain are useful, for example, N,N-dimethylp-xylylenediamine.

Examples of polyamines containing solely secondary amino groups include the following:

H N C aHuN C aHaN CzHrOH |JHz-CH3 N NH HNR wherein R is a hydrocarbon group,

(REF-OH; N NE f HN(oH,NH),H

where z=15 2-undecylimidazoline Z-heptadecylimidazoline 2-oleylirnidazoline 1-N-decylaminoethyl,Z-ethylimidazoline 2-methy1, 1-hexadecylaminoethylaminoethylimidazoline l-dodecylaminopropylimidazoline 1- stearoyloxyethyl) aminoethylimidazoline l-stearamidoethylaminoethylimidazoline 2-heptadecyl,4-5-dimethylimidazoline 1-dodecylaminohexylimidazoline 1-stearoylethylaminohexylimidazoline 2-heptadecyl,l-rnethylarninoethyl tetrahydropyrimidine 4-methyl,2-d0decyl,'1-methylaminoethylaminoethyl tetrahydropyrimidine NCH2 N-GHQ 0 1L011 As previously stated, there must be reacted at least one mole of polyamine per equivalent of methylol group. The upper limit to the amount of amine present will be determined by convenience and economics, for example, 1 or more moles of polyamine per equivalent of methylol group can be employed.

The following examples are illustrative of the preparation of the polyaminomethylol phenol condensate and are not intended for purposes of limitation.

The following general procedure is employed in preparing the polyamine-methlyol condensate. The methylolphenol is generally mixed or slowly added to the polyamine in ratios of 1 mole of polyarnine per equivalent of methylol group on the phenol. However, where the polyamine is added to the methylolphenol, addition is carried out below 60 C. until at least one mole of polyamine per methylol group has been added. Enough of a suitable azeotroping agent is then added to remove Water (benzene, toluene, or xylene) and heat applied. After removal of the calculated amount of Water from the reaction mixture (one mole of water per equivalent of methylol group) heating is stopped and the azeotroping agent is evaporated ofi under vacuum. Although the reaction takes place at room temperature, higher temperatures are required to complete the reaction. Thus, the temperature during the reaction generally varies from -160 C. and the time from 4-24 hours. In general, the reaction can be effected in the lower time range employing higher temperatures. However, the time test of completion of reaction is the amount of water removed.

Example 1a This example illustrates the reaction of a methylolmonophenol and a polyamine. A liter flask is employed with a conventional stirring device, thermometer phase separating trap condenser, heating mantle etc. 70% aqueous 2,4,6 trimethylol phenol which can be prepared by conventional procedures or purchased in the open market, in this instance, the latter, is employed. The amount used is one gram mole, i.e. 182 grams, of anhydrous trimethylol phenol in 82 grams of water. This alter 56 represents three equivalents of methylol groups. This solution is added dropwise with stirring to three gram moles (309 grams) of diethylene triamine dissolved in 100 ml. of xylene over about 30 minutes. An exothermic reaction takes place at this point but the temperature is maintained below approximately 60 C. The temperature is then raised so that distillation takes place with the removal of the predetermined amount of water, i.e., the water of solution as well as water of reaction. The water of reaction represents 3 gram moles or 54 grams.

The entire procedure including the initial addition of the trimethylol phenol until the end of the reaction is approximately 6 hours. At the end of the reaction period the xylene is removed, using a vacuum of approximately 80 mm. The resulting product is a viscous water-soluble liquid of a dark red color.

Example 28a This example illustrates the reaction of a methylolmonophenol and a branched polyamine. A one liter flask is employed equipped with a conventional stirring device, thermometer, phase separating trap, condenser, heating mantle, etc. Polyamine N-400, 200 grams (0.50 mole), is placed in the flask and mixed with 150 grams of xylene. To this stirred mixture is added dropwise over a period of 15 minutes 44.0 grams (0.17 mole) of a 70% aqueous solution of 2,4,6-trimethylol phenol. There is no apparent temperature change. The reaction mixture is then heated to 140 C., refluxed 45 minutes, and 24 milliliters of Water is collected (the calculated amount of water is 22 milliliters). The product is a dark brown liquid (as a 68% xylene solution).

Example 2d This example illustrates the reaction of a methylol diphenol.

One mole of substantially water-free CH2OH CHzOH 3 H OH L O a l (/HsO'H GH2OH and 4 moles of triethylenetetramine in 300 ml. of xylene are mixed with stirring. Although an exothermic reaction takes place during the mixing, the temperature is maintained below 60 C. The reaction mixture is then heated and azeotroped until the calculated amount (72 g.) of water is removed (4 moles of water of reaction). The maximum temperature is 150 C. and the total reaction time is 8 hours. Xylene is then removed under vacuum. The product is a viscous water-soluble liquid.

Example 5b In this example, 1 mole of substantially water-free HOCH; GH2OH is reacted with 2 moles of Duomeen S (Armour Co.),

where R is a fatty group derived firom soya oil, in the manner of Example 2a. Xylene is used as both solvent and azeotroping agent. The reaction time is 8 hours and the maximum temperature ISO-160 c.

' utes.

; amples 1a, 2d, and 5b are also shown in the tables.

1 5 Example 28b This experiment is carried out in the same equipment as is employed in Example 28a except that a 300 milliliter fiask is used. Into the flask is placed 50 grams of xylene and 8.4 grams (0.05 mole) of 2,6-dimethylol-4- methylphenol are added. The resulting slurry is stirred and warmed up to 80 C. Polyamine N-400, 40.0 grams (0.10 mole )is added slowly over a period of 45 min- Solution takes place upon the addition of the polyamine. The reaction mixture is refluxed for about 4 hours at 140 C. and 1.8 milliliters of Water is collected, the calculated amount. The product, as a xylene solution, is a brown liquid.

Example 29b This experiment is carried out in the same equipment and in the same manner as is employed in Example 28b. To a slurry of 10.5 grams (0.05 mole) of 2,6-dimethylol- 4-tertiarybutylphenol in 5 0 grams of xylene, 40 grams (0.10 mole) of Polyamine N-400 are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 4 hours with the collection of 1.6 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is reddish brown.

Example 30b This experiment is carried out in the same equipment and in the same manner as is employed in Example 281'). To a slurry of 14.0 grams of 2,6-dirnethylol-4-nonylphenol in 50 milliliters of benzene, 40.0 grams (0.10 mole) of Polyamine N-400 are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 6 hours with the collection of 1.8 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is dark brown.

The following amino-methylol condensates shown in Tables LIV are prepared in the manner of Examples la, 2d, and 5b. In each case one mole of polyamine per equivalent of methylol group on the phenol is reacted and the reaction carried out until, taking into consideration the water originally present, about one mole of water is removed for each equivalent of methylol group present on the phenol.

The pH of the reaction mixture is determined solely by the reactants (i.e., no inorganic base, such as Ca(OH) NaOH, etc. or other extraneous catalyst is present). Ex- Attempts are made in the examples to employ commercially available materials where possible.

In the following tables the examples will be numbered by a method which will describe the nature of the product. The polyamine-methylol condensate will have a basic number, for example, la, 4b, 6c, 4d, wherein those in the A series are derived from TMP, the E series from DMP, the C series from trimethylol cardanol and side chain hydrogenated cardanol (i.e., hydrocardanol), and the d series from the tetramethylol diphenols. The basic number always refers to the same amino condensate. The symbol A before the basic number indicates that the polyamine had been acylated prior to condensation. The symbol A after the basic number indicates that acylation takes place after condensation.

A25a means that the 25a (amino condensate) Was prepared from an amine which had been acylated prior to condensation. However, IOaA means that the condensate was acylated after condensation. The symbol 0 indicates TABLE IV-Cutinued [Molar ratio of tetramethylol diphenol to polyamine 1 4] Example R Polyamine 18d Methyl-.- Duomeen 'l (Armour 00.)

H RN-CH2 CHzQHzNHz R derived from tallow Oxyethylated Duomeen S do Oxyethylated Duomeen T d0 Amine ODT (Monsanto) Oxyethylated Amine ODT C 2H4 O H The products formed in the above Table IV are dark, viscous liquids.

THE ACYLATIN G AGENT As in the reaction between the methylol phenol and the secondary amine, acylation is also carried out under dehydrating conditions, i.e., water is removed. Any of the well-known methods of acylation can be employed. For example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., are all satisfactory.

A wide variety of acylating agents can be employed. However, strong acylating agents such as acyl halides, or acid anhydrides should be avoided since they are capable of esterifying phenolic hydroxy groups, a feature which is undesirable.

Although a wide variety of carboxylic acids produce excellent products, in our experience monocarboxy acids having more than 6 carbon atoms and less than 40 carbon atoms give most advantageous products. The most common examples include the detergent forming acids, i.e., those acids which combine with alkalies to product soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturally occurring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat diiferent sources and are different in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valeric, caproic, heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, angelic, tiglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid,

the heptenoic acids, the octenoic acids, the noneuoic acids, the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodecenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadccenoic acids, the hexadecenoic acids, for example, palmitoleic acid, the heptadecenoic acids, the octodecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetracosenoic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadieuoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudoeleostearic acid, and the like.

Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hydroxyheptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxymyristic acids, the hydroxypentadecanoic acids, the hydroxypalmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, riciuoleic acid, ricinelardic acid, hydroxyoctadeceuoic acids, for example, ricinstearolic acid, the hydroxyeicosanoic acids, for example,

hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydrocarpic and chaulmoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fencholic acids, and the like.

Examples of aromatic monocarboxylic acids are benzoic acid, substituted benzoic acids, for example, the toluic acids, the xylenic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan wax, Japan Wax, coccerin and carnauba wax. Such acids include caruaubic acid, cerotic acid, lacceric acid, montanic acid, psyllasteric acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from paraffin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesacenic, citraconic, glutaconic, itaconic, muconic, aconitic acids, and the like.

Examples of aromatic polycarboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof, (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two carboxylic groups are hemimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric and polymeric acids, for example, dilinoleic trilinoleic, and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as esters, glycerides, etc. can be employed in place of the free acid.

The moles of acylating agent reacted with the polyaminomethyl compound will depend on the number of acetylation reactive positions contained therein as well as the number of moles one wishes to incorporate into the molecule. We have advantageously reacted 1 to 15 moles of acylating agent per mole of polyaminophenol, but preferably 3 to 6 moles.

The following examples are illustrative of the preparation of the acylated polyaminomethyl phenol condensate. The following general procedure is employed in acylating. The condensate is mixed with the desired ratio of acid and a suitable azeotroping agent is added. Heat is then applied. After the removal of the calculated amount of water (1 to 2 equivalents per mole of acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from 80200 C. (except where the formation of the cyclic amidine type structure is desired and the maximum temperature is generally 200 280 C.). The times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of Water removed.

Example 3aA In a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle, 697 grams of 3a (one mole of the TMP-tetraethylene pentamine reaction product) is dissolved in 600 ml. of xylene. 846 grams of oleic acid (3 moles) is added to the TMP-polyamine condensate with stirring in ten minutes. The reaction mixture Was then heated gradually to about 145 in half an hour and then held at about 160 over a period of 3 hours until 54 grams (3 moles) of water is collected in the side of the tube. The solvent is then removed with gentle heating under a reduced pressure of approximately 20 mm. The product is a dark brown viscous liquid with a nitrogen content of 14.5%.

Example 3aA' The prior example is repeated except that the final reaction temperature is maintained at 240 C. and 90 grams (5 moles) of water is removed instead of 54 grams. Infrared analysis of the product indicates the presence of a cyclic amidine ring.

Example 70A The reaction product of Example 7a (TM? and oxyethylated Duomeen S) is reacted with palmitic acid in the manner of Example 3aA. A xylene soluble product is formed.

The following examples of acylated polyaminomethyl phenol condensates are prepared in the manner of the above examples. The products obtained are dark viscous liquids.

Example 28aA Into a 300 milliliter flask, fitted with a stirring device, thermometer, phase separating trap, condenser and heating mantle, is placed a xylene solution of the product of Example 28a'containing 98.0 grams (0.05 mole) of the reaction product of 2,4,6-trimethylolphenol and Polyarnine N-400 and about 24 grams of xylene. To this solution is added with stirring 40.0 grams (0.15 mole) of lauric acid. The reaction mixture is heated for about one 5 hour at a maximum reaction temperature of 190 C. and 6 milliliters of water are collected. The calculated amount of Water for imidazoline formation is 5.4 milliliters. The resulting product as an 88 percent xylene solution is a dark brown thick liquid.

Example 2812A Into a 300 milliliter flask, fitted with a stirring device, thermometer, phase separating trap, condenser and heating mantle is placed a xylene solution of the product of Example 28b containing 35.0 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-methylphenol and Polyamine N-400 and about 20 grams of xylene. To this solution is added with stirring 30.0 grams (0.15 mole) of oleic acid. The reaction mixture is heated at reflux for 4.5 hours at a maximum temperature of 183 C. and 1.0 milliliters of water is collected, the calculated amount of water for amide formation being 0.9 milliliters. The product is a dark burgundy liquid (as 70.5% xylene solution) Example 2917A This experiment is performed in the same equipment and in the same manner as employed in Example 2812A. Into the flask is placed a xylene solution of the product of Example 29b containing 40.9 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-tertiarybutyl phenol and Polyamine N400 and about 47 grams of xylene. To this solution is added with stirring 7.2 grams (0.05 mole) of octanoic acid. The reaction mixture is heated at reflux for 3.75 hours at a maximum temperature of 154 C. and 1.3 milliliters of Water is collected. The calculated amount of water for amide formation is 0.9 milliliters. The product as a 49.82 percent xylene solution was brown.

Example 3012A This experiment is performed in the same manner and in the same equipment as is employed in Example 28bA. Into the flask is placed a xylene solution of the product of Example 30b containing 39.6 (0.025 mole) of the reaction product of 2,6-dimethylol-4-nonylphenol and Polyamine N-400 and about 32 grams of xylene. To this solution is added with stirring 14.2 grams (0.05 mole) of stearic acid. The reaction mixture is heated at reflux for 4 hours at a maximum temperature of 160 C. and 1.0 milliliter of water is collected. The calculated amount of water for amide formation is 0.9 milliliter. The product as a 62.5% xylene solution is a brown liquid.

TABLE V.ACYLATED PRODUCTS OF TABLE I 1 Dilinoleic acid sold by Emery Industries. Naphthenic acid sold by Sun 0 "Company, average molecular weight; 220-230.

TABLE VI.ACYLATED PRODUCTS OF TABLE II Grams of acid used Grams of Example Acid per gramwater mole of removed condensate See footnotes 1 and 2, Table V.

TABLE VII.-ACYLATED PRODUCTS OF TABLE III Grams of acid used Grams of Example Acid per gramwater mole of removed condensate See footnotes 1 and 2, Table V.

TABLE III.ACYLATED PRODUCTS OF TABLE IV Grams of acid used Grams of Example Acid per gramwater mole of removed condensate 1, 128 72 1,123 72 2,272 144 800 72 912 72 1, 024 72 1,128 72 Dimeric 2, 400 72 Sunaptic 1,320 72 240 72 1,128 72 1, 128 72 1,128 72 1, 128 72 2,048 144 9l2 72 1, 128 72 1, 024 72 1,136 72 1,136 72 1,128 72 1, 128 72 1, 12s 72 1, 12s 72 See footnotes 1 and 2, table V.

Reference has been made and reference will be continued to be made herein to oxyalkylation procedures. Such procedures are concerned with the use of monoepoxides and principally those available commercially at low cost, such as ethylene oxide, propylene oxide and butylene oxide, octylene oxide, styrene oxide, etc.

Oxyalkylation is well known. For purpose of brevity reference is made to Parts 1 and 2 of US. Patent No. 2,792,371, dated May 14, 1957, to Dickson, in which particular attention is directed to the various patents which describe typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish extensive information as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.

The following examples illustrate oxyalkylation.

Example IaAO;

The reaction vessel employed is a 4 liter stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means, etc., which are conventional in this type of apparatus. The stirrer is operated at a speed of 250 rpm. Into the autoclave is charged 1230 grams (1 mole) of MA, and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring started immediately, and heat applied. The temperature is allowed to rise to approximately C. at which time the addition of ethylene oxide is started. Ethylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 132 grams (3 moles) of ethylene oxide is added over 2%. hours at a temperature of 100 C. to C. and a maximum pressure of 30 p.s.i.

Example IaAO The reaction mass of Example 1A0 is transferred to a larger autoclave (capacity 15 liters) similarly equipped. Without adding any more xylene the procedure is repeated so as to add another 264 grams (6 moles) of ethylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.

Example 1aAO In a third step, another 264 grams (6 moles) of ethylene oxide is added to the product of Example laAO The reaction slows up and requires approximately 6 hours, using the same operating temperatures and pressures.

Example 1aAO At the end of the third step the autoclave is opened and 25 grams of sodium methylate is added, the autoclave is flushed out as before, and the fourth and final oxyalkylation is completed, using 1100 grams (25 moles) of ethylene oxide. The oxyalkylation is completed within 6 /2 hours, using the same temperature range and pressure as previously.

Example 1aA0 The reaction vessel employed is the same as that used in Example laAO. Into the autoclave is charged 1230 g. 1 mole) of laA and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring is started immediately, and heat is applied. The temperature is allowed to rise to approximately 100 C. at which time the addition of propylene oxide is started. Propylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 174 a (3 moles) of propylene oxide are added over 2% hours at a temperature of 100 to 120 C. and a maximum pressure of 30 lbs. p.s.i.

Example 1 aAO The reaction mass of Example 1aAO is transferred to a larger autoclave (capacity 15 liters). The procedure is repeated so as to add another 174 g. (3 moles) of propylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.

27 28 Example 1aAO TABLE XII.THE ox i g lgY LArnn PRODUCTS OF v At the f of the Second p p 4 2) the [Grams of oxide added per gram-mole of condensate] autoclave is opened, 25 g. of sodium methylate is added, and the autoclave is flushed out as before. Oxyalkylar Example Eto Pro Buo octylene styrene tion is continued as before until another 522 g. (9 moles) Q oxide oxide of propylene oxide are added. 8 hours are required to complete the reaction.

The following examples of oxyalkylation are carried out in the manner of the examples described above. A catalyst is used in the case of oxyethylation after the initial moles of ethylene oxide are added, while in the case of oxypropylation, the catalyst is used after the initial 6 moles of oxide are added. In the case of oxybutylation, oxyoctylation, oxystyrenation, etc. the catalyst is added at the beginning of the operation. In all cases the amount of catalyst is about 1 /2 percent of the total reactant present. The oxides are added in the order given reading from left to right. The results are presented in the following tables:

TABLE IX.-THE OXYALKYLATED PRODUCTS OF TABLE I TABLE XIII.THE OXYA [Grams of oxide added per grarnmole of condensate] OF TAB IL K E X PRODUCTS [Grams of oxide added per gram-mole of condensate] Example EtO PrO BuO Octylene Styrene oxide oxide Example EtO PrO BuO Octylene Styrene oxide oxide TABLE X.THE OXYALKYLATED PRODUCTS OF TABLE II {Grams of oxide added per gram-mole of condensate] TABLE XIV.-THE OXYALKYLATED PRODUCTS OF Example EtO PrO BuO Octylene Styrene TABLE VI oxide oxide [Grams of oxide added per gram-mole of acylated product] Octylene Styrene oxide TABLE XI' THE OXYALKYLATED PRODUCTs OF TABLE XV.THE OXYALKYLATED PRODUCTS OF TABLE III TABLE VI [Grams of oxide added per grammlole of condensate] [Grams of oxide added per grarn-mo1e oi acylated product] Example EtO PrO B110 Oetylene St ene Exam le EtO PrO But) Octylene Styrene Y p oxide oxide oxide .Okide OXYALKYLATED PRODUCTS F TABLE VII [Grams of oxide added per gram-mole of aeylated product] EtO PrO BuO Oetylene oxide oxide Since the oxyalkylated, and the acylated and oxalkylated products have terminal hydroxy groups, they can be acylated. This step is carried out in the manner previously described for acylation. These examples are illustrative and not limiting.

Example IaOA One mole (919 grams) of MO mixed with 846 grams (three moles) of oleic acid and 300 ml. xylene. The reaction mixture is heated to about ISO-160 C. over a period of 2 hours until 54 grams (3 moles) of water are removed. Xylene is then removed under vacuum. The product laOA is Xylene soluble.

Example JaA A The process of the immediately previous example is repeated using laAO. The product laAOA is Xylene soluble.

Additional examples are presented in the following tables. All of the products are dark, viscous liquids.

TABLE XVII.-THE ACYLATEDUT RODUCTS OF TABLES IX TABLE XVIIL-THE ACYLATED PRODUCTS OF TABLES XIII, XIV, XV, XVI

Grams of acid per Grams gram-mole water Example Acid oi oxyalkylremoved ated product 282 18 284 18 282 18 284 18 200 18 282 18 V 282 18 Stearic 284 18 Olpin 282 18 Stearic 284 18 Oleic 564 36 d 282 18 Myrist1e 228 18 Laurie 200 18 Oleie 282 18 .d 282 18 Steano 568 36 568 36 Oloic 564 36 d0 564 36 AGENTS FOR SCALE PREVENTION This phase of the invention relates to the use of the aforementioned compounds in a process for removing from surfaces, particularly of pipes and other processing equipment, deposits of inorganic solids arising from the passage of aqueous media therethrough, and for inhibiting and preventing the accumulation of such deposits on such surfaces. They are particularly adapted for use in equipment used in producing and handling crude oil, since the water produced from the earth along with the oil often deposits inorganic solids as a scale in the well tubing, or, more commonly, in traps, heaters, or other surface equipment, and in some instances even in pipelines. They are likewise valuable in controlling deposits or scales of such inorganic solids which may accumulate in steam-generating equipment if somewhat hard waters are used. Utility of these compounds is not limited to such characteristic applications; they may be used in other instances Where scales or deposits of inorganic solids originating from naturally-occurring constituents of aqueous media constitute a nuisance in industrial or other activities.

The scales or deposits of inorganic solids that occur in hard Water with which this invention is concerned are clearly to be distinguished from accumulations of solid organic matter, whose removal is the subject-matter of Patent No. 2,470,831, dated May 24, 1949.

The accumulations with which this phase of the present invention is concerned are also to be distinguished at the outset from accumulations of mud solids in the form of mud sheaths. Mud sheaths are essentially filter cakes of water-insoluble solids of natural clay solids or of barite, iron oxide, bentonite, or other inorganic solids used in preparing and conditioning drilling mud and originally present as an aqueous suspension. The inorganic solids with which the present invention is concerned may be thought of as being originally water-soluble inorganic solids which have been precipitated as hard-water scale by the application of heat, the loss of carbon dioxide or some other constituent, or in some cases by the chilling of the aqueous medium as it passes through the conduit or apparatus which exhibits the scaling, etc. Accumulations of such solids are recurring problems.

The process which constitutes this phase of our invention consists in applying to inorganic solid deposits of the kind described the compounds of the present invention to the end that such inorganic solids are removed from the surfaces to which they originally adhered. By such means, the capacity of pipes, towlines, pipelines, traps, tanks, pumps, and other equipment supporting such deposits is materially increased. The exact nature of the 31 action taking place when our reagents are used is unknown to us.

It will be apparent that if our reagents are applied to a system which periodically accumulates such deposits of inorganic solids, before appreciable deposition has occurred, and if such application of reagents is practiced continuously or with suificient frequency, the operation may be considered a preventive process, rather than a corrective one. If applied in somewhat insuificient quantity to a deposit already accumulated it may accomplish partial reduction of such deposit, rather than complete removal. Our process is therefore both a preventive and a corrective one, and may be applied in either sense, to achieve the same ultimate goal, viz., improvement of the capacity of conduits through which fluids are passed.

Our process is equally applicable to systems in which a deposit of inorganic salts is already in existence and to systems which are potentially susceptible to such deposition. When we use the Word inhibiting, we mean to include therein the prevention, reduction, and removal of such deposits of inorganic solids.

These compositions are usually used diluted with a suitable diluent, such as water or a water-insoluble organic liquid capable of acting as an oil solvent.

In treating systems in which oil is present, we prefer to mix the compounds with a Water-insoluble organic liquid capable of acting as an oil solvent, and to employ such mixture in the form of a relatively stable aqueous dispersion. By relatively stable aqueous dispersion, we mean one that is not resolved into its components spontaneously on standing for protracted periods of time, e.g., for more than one hour. However, such preferred mixture may be employed undiluted or dispersed in oil. These compounds may be mixed with water, especially if in salt form, to produce a relatively stable aqueous dispersion, and may be used as such or diluted further with Water. In general, we believe the form of the reagent in which a water-insoluble organic liquid is incorporated gives superior results, at least where the system to be treated includes oil.

Some of the compounds of our invention are freely dispersible in water in the free state. In other instances, the free forms of the reagents are substantially waterinsoluble, but the salt forms (e.g., the acetates) are very water-dispersible. We prefer to employ the water-dispersible form by neutralizing the compound to produce a salt which will be Water-dispersible. We have found, for example, that the acetate, hydroxyacetate, lactate, gluconate, propionate, caprate, phthalate, fumarate, maleate, benzoate, succinate, oxalate, tartarate, chloride, nitrate, or sulfate, prepared by addition of the suitable acid to the compound, usually constitutes a reagent which is somewhat more soluble or dispersible in water than many of the original compounds. It is to be understood that references to the reagents, in these specifications and claims, include the reagent in the form of salts, as well as in the free form and the hydrated form.

Depending upon the choice of compound and its molec ular weight, the solubility may be expected to range from ready water-solubility in the free state substantially to water-insolubility. As stated above, the salts, and specifically the acetates, generally show improved water-solubility over the simple compound and we have obtained the best results by using salt forms which possess appreciable water-solubility.

For a number of reasons it is usually desirable to mix the compounds with a suitable diluent before use in our process. Water is sometimes the most desirable diluent, being cheap and available. In some instances, as above noted, especially where the scale-susceptible system includes oil we prefer to use a Water-insoluble organic liquid, which is capable of acting as an oil solvent, for the diluent. Many materials lend themselves to this use. One of the most common is the aromatic fraction of petroleum dis- ;tillates. Edeleanu extract, which comprises aromatic and unsaturated compounds, is frequently found useful. In some cases stove oil or a similar petroleum distillate is usable. Oil solvents like carbon tetrachloride or carbon disulfide are usable, although their comparatively high cost militates against their use. Amylene dichloride is sometimes a desirable material for the present purpose, as are tetrachloroethane, tetraline, trichloroethylene, benzol and its homologs, cyclohexane, etc. This component of our reagents should naturally be compatible with the other ingredient thereof; otherwise its selection is not limited. Cost and availability will influence the selection. We prefer to use an aromatic petroleum solvent as a widely available reagent of good properties and low cost for the present use.

To prepare our reagents, when diluents are included, the components are simply mixed together in suitable proportions. The optimum proportion of each will vary, depending on its properties; but in general the resulting mixture should be homogeneous.

We also require that the finished reagent produce a relatively stable aqueous dispersion. In cases where the ingredients form thoroughly homogeneous mixtures which are not water-dispersible, the transformation of the reagent into its salt form will sometimes accomplish this purpose. In such cases, we have preferably used acetic acid to effect this neutralization.

The reagent may be employed in undiluted form, except for the dilution employed in manufacture, to deliver it in readily usable form. In such cases, the reagent as compounded is simply introduced into the pipe or apparatus from Whose surface a deposit or scale of inorganic solids is to be removed or deposition thereon inhibited. In such cases, there is undoubtedly produced an aqueous dispersion of the reagent if Water is present in or passing through such apparatus. Such addition of undiluted reagent into a stream containing aqueous components may be considered equivalent to introducing a previously prepared aqueous dispersion of my reagent.

In most cases, an aqueous dispersion is obtained almost spontaneously on mixing with water our reagents and preferred non-aqueous diluent. We prefer to employ such embodiments of our reagents in aqueous dispersion, because, when so employed, the components of the reagent are prevented from separating from each other by the'influence of oily materials present in the pipe or apparatus to be treated.

When a water-insoluble organic liquid is employed as diluent in preparing our reagents, We prefer to employ a considerable excess of reagent over what would be exactly required to eifect dispersion of the water-insoluble organic liquid in water. Such excess further prevents any separation of the phases, enhancing the stability of the dispersion so that it will remain stable for at least several hours. The excess of reagents also acts to lower the surface tension of the whole reagent, because of which the reagent exhibits a marked penetrating effect. In this way, it is carried into the crevices and irregularities of the deposit, weakening the bond between the deposit of inorganic solids and the supporting wall.

As a preferred example of reagent, we employ a 20% by weight dispersion in aromatic petroleum solvent, including 2% by weight of concentrated acetic acid in the finished reagent in some instances. We prefer to employ this reagent in the form of a dilute aqueous dispersion, of about 5% by weight concentration. Sometimes aqueous dispersions containing as little as 1% of the reagent are fully effective. Sometimes it is desirable to introduce the reagent in the form of a more concentrated aqueous dispersion, as when additional water is expected to be encountered in the system being treated. This preferred reagent may of course be introduced in undiluted form, if desired, it has been successfully so used.

From the foregoing, it will be understood that our process, broadly stated, consists in subjecting a deposit of inorganic solids of the kind described above to the action of a reagent of the kind described. Merely introducing our reagent continuously into a scaled-up system usually results in the more or less complete removal of the scale Within a reasonable time. Agitating the reagent in the system sometimes facilitates removal of the scale deposits, as does allowing the reagent to stand in the system and soak it for any desired time.

The theory of the mode of operation of our process is uncertain; but the eifects of applying the process are striking. Capacity of pipes and apparatus is usually promptly and markedly increased. Line pressures which have increased with deposition of the inorganic solids fall to normal within a short time; and sometimes sizeable chunks of the dislodged deposit are observed in the stream from the wells or lines, on screens inserted into such streams for purposes of observation, or even, at times, by their erosive effects on valves or other equipment downstream the deposit.

Our reagents may be applied in many ways, depending on the location and character of the deposit of inorganic solids it is proposed to remove or whose deposition is to be inhibited. In the case of pipe, it is usually preferred to introduce, by means of a small proportioning pump, a continuous small stream of reagent, either undiluted or diluted as desired, upstream the deposit, until the latter is dislodged and removed. In some apparatus, it is most practicable to fill the whole with an aqueous solution or dispersion of the reagent, and allow a considerable soaking period to elapse before again pumping. As stated above, we prefer to introduce our reagents in aqueous dispersion, and continuously in small proportions, to inhibit or to remove inorganic solid deposits of the kind here under consideration. The essential step of our process is that our reagent is brought into contact with the deposit; and the latter is thereby caused to become dislodged from is supporting surface.

The following specific examples will illustrate typical applications of our process.

Example 8-1 The surface flow system from an oil Well regularly accumulates a hard scale which includes an appreciable proportion of carbonates precipitated from the oil well water as a compact, adherent deposit, reaching thicknesses of /4 or greater, in the header manifolds, trap valves, rundown lines, etc. Trap valves at the highand low-pressure traps are favorable observation points, in that they scale-up soonest after cleaning. General practice at the location is to produce the well as long as possible, shut down, and then remove the scale manually from all accessible locations in the system. The operation is required to be repeated at intervals of about three weeks.

A reagent comprising a 20 weight percent solution of compound 8-1 of the following table in an aromatic solvent is introduced continuously into the system upstream the high-pressure trap at the rate of 1 gallon to 1,500 barrels of water produced by the well. Inspection of accessible points, which normally scale-up within three Weeks, is made regularly from the beginning of such application of reagent. After about a month, inspection shows a slight deposit of solids on the trap valves, very soft and readily removable. Three months later, the injection of reagent is still continuing, the well having never been shut down for scale removal, and there is no evidence of appreciable scale accumulation in the system.

Example 8-2 This example is cited to illustrate the removal approach, rather than the inhibition or prevention approach of the previous example.

An oil Well production system has accumulated scale to the point where it could handle only about 9,000 barrels of fluid daily, against a rated capacity of 12,000 barrels daily. An attempt to increase the flow through the traps caused them to pop their contents of crude oil.

The compound of 82 (20 Weight percent solution in aromatic solvent) is injected at the Well head, just downstream the floW beam, after preliminary inspection of the degree of scale deposition has been made. Such inspection shows that flow valves upstream the master trap, the manifold, and also the trap discharge valve are heavily scaled. The rate of reagent feed is 1 gallon to 1,500 barrels of well water. Within a week after introduction of our reagent has begun, sustained unrestricted flow at 12,000 barrels daily is again effected.

Re-inspection of accessible points shows some of them to be entirely free from scale deposits, points previously scaled hard. In other cases, the scale has not been entirely removed in the short time of application of our reagent; but the remaining accumulations are very soft in character.

This second example illustrates the fact that our process may be successfully applied as a scale-removing process; and the fact that incomplete removal is found at several points in the system after a short period of treatment illustrates the scale-reduction feature of our process.

Example 8-3 In a third application of our process, we employ compound 8-3 in the form of the acetate, prepared as a 20 weight percent aromatic solvent solution diluted with water to a 15% solution. This material is introduced into a pipe carrying oil and water at the rate as in the preceding two examples. Such introduction effectively inhibits the accumulation of scale in such pipe.

Examples of compounds capable of being similarly employed are shown in the following table.

SCALE REMOVER Ex. Weight of oxides added N0. H2O elimto I (grams) Reactants (grams) inated 81 1a(g%329)+0lelc acid 18 None. s-2 1a (2%]?6O5-l-lauric acid is Do. s- 2a (5685+1amic acid 18 Do. s-4--- 1oa oi5 +1auiic acid 18 Do. s-s--- 1b(492' +cicic acid is Do. 86 3b(5g2')+c1aic acid is Do. s- 4c g sh-1mm acid is Do. s-s.-- 1d ss03+suna tic is Do.

acid 330 8- 16 (i2(()%l0)+lauric acid 18 Do. 23-10-- 1a ggQS-l-Meic acid 18 Et0(880). 841.. 1a 48g9+oleic acid 18 Et0(1320). 3-12 1b923+01eic acid 18 Et0(1100). 843-- 4c (270?;3) +lauric acid is Et0(1320). s-14 1d(660 )+sunaptic 18 EtO(1760).

acid (330 24-15-- lfitfiOQ-I-lauric acid 18 Et0(1320). s-1s 28a (1960 A)Pr0(580). 23-17-- 2s g 9eo +1auric acid (A)Pr0(116) (B)Et0(l320). s-1s 28a0 iioso+sicaric 1s acid (284). 849-. 28aAOA s-20 28b(1400) mousse 22-21-. 28l(o5i)400)+oleic acid 40 Et0(2640). s 22 zsbAoii 51-23-- 29b (1635) (A)Pr0(522) (B)Et0(l980). s-24- 29l(oglfi35)+oleic acid is EtO(1320). s-25 29100 s55 +o1cic 1s acid (282). 8%.. ZQbAOA s-27 30b (1580) Et0(2200). s-2s 30b (l580)+stearic 40 acid (569). 23-29-. 30b (1580)+stcaric 4o (A)PI"O(454) (B)Et0(1320).

acid (569). 23-30 30bAOA We claim:

1. A process for preventing, reducing and removing the deposition of hard-Water scale from the surfaces of equipment of an aqueous scale-forming media system which includes applying to said system in an amount sufficient to prevent, reduce and remove deposition of hard-water scale a member selected from the group consisting of:

(1) acylated, (2) oxyalkylated, (3) acylated then oxyalkylated, (4) oxyalkylated then acylated, (5) acylated, then oxyalkylated and then acylated, monomeric polyaminomethyl phenols characterized by reacting a preformed methylol phenol having one to four methylol groups in the 2,4,6 position with a polyamine containing at least one secondary amine group in amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol until one mole of water per equivalent of methylol group is removed, in the absence of an extraneous catalyst; and then reacting the thus formed monomeric polyaminomethyl phenol with a member selected from the group consisting of (1) an acylation agent, (2) an oxyalkylation agent, (3) an acylation then an oxyalkylation agent, (4) an oxyalkylation then an acylation agent, and (5) an acylation then an oxyalkylation and then an acylation agent the preformed methylol phenol having only functional groups selected from the class consisting of methylol groups and phenolic hydroxyl groups, the polyamine having only functional groups selected from the class consisting of primary amino groups, secondary amino groups and hydroxyl groups, the acylation agent having up to 40 carbon atoms and being selected from the class consisting of unsubstituted carboxylic acids, unsubstituted hydroxy carboxylic acids, unsubstituted acylated hydroxy carboxylic acids, lower alkanol esters of unsubstituted carboxylic acids, glycerides of unsubstituted carboxylic acids, unsubstituted carboxylic acid chlorides and unsubstituted carboxylic acid anhydrides, and the oxyalkylation agent being selected from the class consisting of alpha-beta alkylene oxides and styrene oxide.

2. The process of claim 1 where the preformed meth ylol phenol has all available ortho and para positions substituted with methylol groups.

3. The process of claim 1 where the polyamine is an aliphatic polyamine.

4. The process of claim 1 where the polyamine is a polyalkylene polyamine.

5. The process of claim 1 where the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms.

6. The process of claim 1 where the oxyalkylation agent is at least one 1,2-alkylene oxide having 2 to 4 carbon atoms.

7. The process of claim 1 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, the acylation agent is a monocarhoxy acid having 7 to 39 carbon atoms, and the oxyalkylation agent is at least one 1,2-alkylene oxide.

8. The process of claim 1 Where the member is an acylated monomeric polyaminomethyl phenol.

9. The process of claim 1 where the member is an acylated then oxyalkylated monomeric polyaminomethyl phenol.

10. The process of claim 8 Where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, and the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms.

11. The process of claim 9 where the preformed meth ylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms, and the ox alkylation agent is at least one 1,2-alkylene oxide.

12. The process of claim 10 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is diethylene triamine, and the acylation agent is oleic acid.

13. The process of claim 10 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is triethylene tetramine, and the acylation agent is oleic acid.

14. The process of claim 11 where the preformed meth ylol phenol is 2,4,6-trimethylol phenol, the polyamine is diethylene triamine, the acylation agent is oleic acid, and the oxyalkylation agent is at least one 1,2-alkylene oxide having 2 to 4 carbon atoms.

15. The process of claim 11 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is triethylene tetramine, the acylation agent is oleic acid, and the oxyalkylation agent is at least one 1,2-alkylene oxide having 2 to 4 carbon atoms.

16. The process of claim 14 Where the 1,2-alkylene oxide is ethylene oxide.

17. The process of claim 15 where the 1,2-alkylene oxide is ethylene oxide.

References Cited in the file of this patent UNITED STATES PATENTS 2,341,907 Cheetham et al Feb. 15, 1944 2,589,195 Monson Mar. 11, 1952 2,763,680 Sallman Sept. 18, 1956 2,792,359 De Groote May 14, 1957 2,907,778 Greenlee Oct. 6, 1959 2,907,791 Schmidt et al Oct. 6, 1959 2,946,759 Gallant et al. July 26, 1960 

1. A PROCESS FOR PREVENTING, REDUCING AND REMOVING THE DEPOSITION OF HARD-WATER SCALE FROM THE SURFACES OF EQUIPMENT OF AN AQUEOUS SCALE-FORMING MEDIA SYSTEM WHICH INCLUDES APPLYING TO SAID SYSTEM IN AN AMOUNT SUFFICIENT TO PREVENT, REDUCE AND REMOVE DEPOSITION OF HARD-WATER SCALE A MEMBER SELECTED FROM THE GROUP CONSISTING OF: (1) ACYLATGED, (2) OXYALKYLATED, (3) ACYLATGED THEN OXYALKYLATED, (4) OXYALKYLATED THEN ACYLATED, (5) ACYLATED, THEN OXALKYLATED AND THEN ACYLATED, MONOMERIC POLYAMINOMETHYL PHENOLS CHARACTERIZED BY REACTING A PREFORMED METHYLOL PHENOL HAVING ONE TO FOUR METHYLOL GROUPS IN THE 2,4,6 POSITION WITH A POLYAMINE CONTAINING AT LEAST ONE SECONDARY AMINE GROUP IN AMOUNTS OF AT LEAST ONE OME OF SECONDARY POLYAMINE PER EQUIVALENT OF METHYLOL GROUP ON THE PHENOL UNTIL ONE MOLE OF WATER PER EQUIVALENT OF METHYLOL GROUP IS REMOVED, IN THE ABSENCE OF AN EXTRANEOUS CATALYST; AND THEN REACTING THE THUS FORMED MONOMERIC POLYAMINOMETHYL PHENOL WITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF (1) IN ACYLATION AGENT, (2) AN OXYALKYLATION AGENT, (3) AN ACYLATION THEN AN OXYALKYLATION AGENT, (4) AN OXYALKYLATION THEN AN ACYLATION AGENT, AND (5) AN ACYLATION THEN AN OXYALKYLATION AND THEN AN ACYLATION AGENT THE PREFORMED METHYLOL PHENOL HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF METHYLOL GROUPS AND PHENOLIC HYDROXY GROUPS, THE POLYAMINE HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF PRIMARY AMINO GROUPS, SECONDARY AMINO GROUPS AND HYDROXYL GROUPS, THE ACYLATION AGENT HAVING UP TO 40 CARBON ATOMS AND BEING SELECTED FROM THE CLASS CONSISTING OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED HYDROXY CARBOXYLIC ACIDS, UNSUBSTITUTED ACYLATED HYDROXY CARBOXYLIC ACIDS, LOWER ALKANOL ESTERS OF UNSUBSTITUTED CARBOXYLIC ACIDS, GLYCERIDES OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED CARBOXYLIC ACID CHLORIDES AND UNSUBSTITUTED CARBOXYLIC ACID ANHYDRIDES, AND THE OXYALKYLATION AGENT BEING SELECTED FROM THE CLASS CONSISTING OF ALPHA-BETA ALKYLENE OXIDES AND STYRENE OXIDE. 